Fungicidal materials



Patented Dec. 12, 1944 FUNGICIDAL MATERIALS GeraldH. Coleman and Gerald A. Griess, Midland, Mich, assignors to The Dow Chemical Company, Midland, Mich., a corporation of Michigan No Drawing. Application October 30, 1943,

Serial No. 508,377

12 Claims. (Cl. 167-31) The present invention is concerned with new fungicidal materials and is particularly directed to fungicidal compositions comprising inert diluents and as active toxic ingredients certain amine salts of halo-phenols, and to the compounds so employed.

ganisms.

like.

longed effect is desired.

relatively innocuous to humans.

We have discovered that improved fungicidal compositions are obtained when an inert diluent is compounded with certain amine salts of halophenols. These salts are in themselves novel and are characterized by the following formula:

R'CaH1o-NH3w['(C Him-" viiw (cyclic) l The 6 wherein R. represents an aromatic radical of the Phenols and particularly halmphenols and benzene series, R represents an alkyl radical of their metal salts have been widely employed as from 1 to 8 carbcm atm,s'inh.1sivepheny1cycloconstituents of fungicidal compositions. For hexyl' hydrogen w 15 an Integer i such operations as wood preservation and slime n m s an integer not greater t an 18 control, Where there is no problem of injury with an integer from 2 to inclusive t Z at 2 orespect to the material treated, these compounds i h rg g g g gz fi 55,2 3; have been found satisfactory toxicants for con- Z6 9 av ng eas trolling a wide range of bacteria and fungus orgg g g z ig ggzfii.g g fig In these applications, the phenolic 15 err em men s o 1 n toxicant generally has been employed in soluble fungicidal compositions i compounds of form and dissolved either in water or in organic 'g g h z' g g gggg fi iggi a solvent such as petroleum oil, naphtha, and the eye 0 exy represen Z represents a polychlorophenyl radical, and n An entirely different situation is encountered is u in the provisionof agricultural fungicides for The expression of the nz sales as apuse on plants, Seeds fruit etc" where the plied to aromatic and halo-aromatic radicals, ceptibmty of the host to injury is a controlling refers to mononuclear aromatic structures charfactor in the selection of the toxicant and type acteflzed by the phenyl ring of composition to be employed. Here, the indiscriminate use of free phenols and their inorganic salts is impossible because of the phytotoxic properties of such compounds whereby roots, leaves, -zigi gg g g 3 13 533351: ggg gggg fisd flowers, fruit, and buds may be severely injured. 1 1 o e 5 cont mm Several benzene Also, the solubility characteristics of the common p0 ynuc ear m m s a g metal salts of phenols are not favorable where nuclei linked together in such a manner that it is desired to maintain the toXicant in con- 2: gz ifsfi g fgfiafi i' ga m comtact with or adjacent to the area of infestation. 5 g amgne li as descriid in'the fore- Rain, heavy dew, subsequent spraying, or irrigtation rapidly disperses such toxicant whereby 85 sggfi fgggg g gg 2g: arg fi z ticz r b s i s continued effect is lost. A similar failure on being less than 0.02 per cent soluble in water at Z3252? 112E355? 5.233 31%! $5635.22??? with the attributable to their high volatility. It is ap- 5: 3: gggg fg shg gfigigfil ,5 3:: parent therefore that many the subtances faces persistent and not inclined to be leached commonly employed i fungwlqal practlce are out bywater or otherwise dissipated. The toxic P i for 3 m H1958 51151131310115 which effect exerted by compositions containing these mvo ve con act in h plant tissue or where a prosalts in mixture with inert diluents is thereby extended over an a reciable riod. Also, the In the selection of toxicants for general fungi- 46 new salt compounds are subst i itially less toxic cidal use,- and more particularly agricultural apt growing vegetation t are t correspondplication, it is desirable that materials be chosen m free phenols or {heir metallic 1t hi ave u hp pe s 'n t t be rapidly compounds and compositions in which theyv are gliissiplated from the pgmt 0f fgpl g o z whereby 5o employed are very effective against a wide range 8 ev p fe a ow of ac eria and of organisms. This would appear to result from fun us organisms is controlled over a lon pethe association in a single molecule of two pher1od of time. It 1s alsodesirable that the chosen noxy groupings, as represented by Z-O- and tox cant be non-corrosive to growing plants and R-O, and the highly substituted cyclohexylammonium radical.

The compounds as set forth above may be employed generally as toxicants in fungicidal mixtures. V They may be used as constituents of either dusting or spraying compositions. Thus, they may be compounded with various finelydivided inert diluents such as diatomaceous earth, bentonite, talc, sulfur, \wood flours, inorganic phosphates, clays, and the like, to form dusts adapted to be applied to plants or other fungus infected objects and surfaces with standard dusting equipment, or otherwise applied as in the resulting dust (0.5 pound of toxicant) and 0.25 pound of sodium lauryl sulfate were then dispersed in 100 gallons of water and the resulting spray composition applied directly to bean foliage for the control of mildew. The results obtained with representative salt compounds when employed in this manner are summarized in the following table:

, Table Compound Pounds per Percent 100 gallons effectiveness Beta-(2.4.6-trichloropbenoxy)-beta'-cyclohcxylamino-diethyl ether salt of pentachlorophenol 0. 5 100 N 2-(2-cycl0hexylphenoxy)ethyl] cyclohexylamine salt of 2.4.6-tr1chlorophenol c. 0. 5 09 N- enXy)-ethyl] Z-methyl-cyclohexylamine salt of 2.4.5-trichlorophenol 0. 9.5 N.N-di-[2-( i-chlorophenoxy)-ethyl] cgclohexylamine salt of pentachlorophenol 0. 5 00 N-[3-(i-tertiarybutylphenoxy)-2'met yl-propyl] cyclohexylamine salt of 2-hydroxy-3.5 trichloro-d pheny 0. 5 0.; Beta-(i-cyclohexylphenoxy)-beta-cyclohexylamino-diethyl ether salt of 2-hydroxy-3.5.x-trichloro-dipheny 0. 5 9.3 N-[3-(4-chlorophenoxy)-2-methyl-propyl] cyclohexylamine salt of 2.3.4.6-tetrachlorophenol 0. 5 100 B8t8-(4-chlorophenoxy)-beta-cyclohexylamino-diethyl ether salt of 2.3.4.6-tetrachlorophenol 0. 5 98 N -[3-(4-tertiarybutylphenoxy)-2-methyl-propyl] cyclohexylamine salt of 2.3.4.6-tetrachlorophenol. 1.0 100 N.N-di-[2-(4-chlorophenoxy)-ethyl] cyclohexylamine salt of 2.3.4.6-tetrachlorophenol i. 5 100 Beta-phenoxy-beta'-cyclohex lamino-diethyl other salt of 2.3.4.6-tetrachlorophenol 1.0 100 N -[2-(4-chl0rophenoxy)ethylfcyclohexylamine salt of 2.3.4.6-tctrachlorophenol 0. 5 97 seed disinfection, etc. If desired, such dusts may be employed as concentrates and subsequently diluted with additional finely-divided carrier, or suspended in water or other inert liquid diluentto form sprays. The amine addition salts may also be incorporated with various wetting, dispersing, and sticking agents, and subsequently diluted to produce spray or dust compositions in which the salt is present in any desired concentration.

In the preparation of concentrates, from about 5 to about 80 per cent of the amine salt is commonly employed. The concentration of the salt in the ultimate spray or dust composition is generally between about 0.01 per cent and 10.0 per cent by weight. For seed disinfection and other general fungicidal use the concentration of the toxicant may run as high as 80 per cent. The composition type in which the salt is employed and the concentration thereof in the final composition are dependent upon the particular bacteria or fungi to be controlled and the circumstances under which such control is to be accomplished.

In other embodiments of the invention the amine salts may be employed in combination with oil emulsions. They may also be employed in water suspension with or without an additional emulsifying, wetting, or dispersing agent. The

amine salt may similarly be incorporated in other standard type fungicidal and bactericidal compositions either as the sole toxic ingredient of such mixture or in combination with such materials as inorganic pigments, organic dyes, sulfur, copper sprays, and the like.

The several examples are illustrative with respect to the particular compounds, composition types, and concentrations employed, but are not to be construed as limiting the invention.

ExAuPLr: 1

A series of determinations were carried out in which a, number of the amine salt compounds were dispersed on a diatomaceous earth product marketed as Celite and employed in aqueous dispersion for the control of bean mildew on bean foliage. In a representative preparation, parts by weight of N-[2-(4-chlorophenoxy)-ethyl] cyolohexylamine salt of 2.3.4.6-tetrachlorophenol was dissolved in acetone and this solution used to moisten 80 parts by weight of the diatomaceous earth. The wet product was mixed andthereafter air-dried to remove acetone, 2.5 pou s Of EXAMPLE 2 In a similar fashion, dust concentrates comprising the amine salts were compounded to form spray compositions and applied to apple foliage for the control of apple scab. In a representative determination the N-[2-(4-chlorophenoxy)-ethyl] cyclohexylamine salt of 2.3.4.6- tetrachlorophenol at 0.5 pound per 100 gallons of spray was per cent effective without injury to the apple foliage.

EXAMPLE 3 Other determinations were carried out in which the dust concentrates were dispersed in water along with 0.5 pound of sodium lauryl sulfate, per gallons and applied for the control of snapdragon rust on snapdragons. When employed in the amount of 1.0 pound per 100 gallons the N-[3-(4 tertiarybutyl-phenoxy) 2- methyl-propyll cyclohexylamine salt of 2.3.4.6- tetrachlorophenol was 88 per cent effective.

EXAMPLE 4 1 part by weight of N-[2-(4-chlorophenoxy)- ethyl] cyclohe ylamine salt of 2.3.4.6-tetrachlorophenol was issolved in acetone and deposited on 99 parts by weight of pyrophyllite (sold as Pyrax). This mixture was dried and the resulting finely-divided composition applied as a dust for the control of a Fomes annosus type organism. This treatment gave 100 per cent control of the organism in a series of three separate determinations.

EXAMPLE 5 10 parts by weight of the N-[2-(4-chlorophenoxy) -ethyl] cyclohexylamine salt of 2.3.4.6-tetrachlorophenol and 5 parts by weight of sodium oleate were dissolved in methanol and the resulting solution used 'to wet 85 parts by weight of loom kiln talc. The wet product was thoroughly mixed and thereafter dried to obtain a dust composition adapted to be employed in the disinfection of seeds. In representative operations this finely-divided material was applied to corn and beans in the amount of 2 ounces per bushel by shaking the seed with the indicated amount of fungicidal mixture. The seeds were then planted in disease-infested soil and the percentage emergence of the treated seed compared with that of untreated seed. The emergence on the treated corn was 70 per cent. The emergence of corn in the control plot was only 49 per cent. With beans the percentage emergence was 70 per cent for the treated seed and only 20 for the untreated.

/ Examern 6 I Dusting compositions comprising the amine salts of halo-phenols astoxic ingredients are illustrated by the following:

Parts by' Compound weight COMPOSITION A N-[2-(2.4-dichlorophenoxy)-propyl] 4-tertiary-butylcyv S cllfohexylamine salt of 2.4.6'tribromophenol 3 u ur COMPOSITION B N-[2-(4-bromophenoxy)ethyl] cyclohexylamine salt of t-iodophenol T Walnut shell flour COMPOSITION C Gamma- (4-chlorophenoxyi -gamma -(4-cyclohexylcyclohexylamino)-dipropyl ether salt of pentachlorophenol.-. Pyrethrum Diatomaceous earth COMPOSITION D Beta-[2-(2-cyclohexylphenoxy)-ethoxy]-heta-(4-phenylcyclohexylamino)-diethyl ether salt oi 2.4.5 ttichlorophenol Suliur Diatornaccous earth COMPOSITION E N.N-di-[2- (2- (2-phenoxy-ethoxy) ethoxy) -ethyl] cyclohcxylamine salt oi pentachlorophenol 5 Red talc 95 The above and related compositions may be applied with standard dusting equipment for the control of been mildew, apple scab, snapdragon rust, tomato leaf spot, and other fungus organisms. Similarly, they are adapted to be used for the control of brown rot and other bactericidal organisms commonly attacking plant tissue.

Examru:

The following are representative of compositions adapted to be employed as general fungicidal materials, preferably as constituents of aqueous spray mixtures.

COMPOSITION G N-[2-(2-benzyl-phenoxy)-ethyl]4tertiaryoctylcyclohexylamine salt of 2.4.6-trichlorophenol l Bentonite 85 Sodium lauryl sulfate The foregoing compositions may be diluted with water to obtain spray mixtures adapted to be applied for the disinfection of stables, chicken yards, soil adjacent to growing plants, and the like.

The new chemical compounds to be applied according to the foregoing examples are readily prepared by warming together a free halo-phenol and a suitable amine. If desired, such reaction can be carried out in an inert organic solvent for the reactants. The temperature of reaction is not critical although best results are obtained at temperatures between about C. and the decomposition temperature of the reactants and amine salt product. The reaction is preferably carried out by adding one of the reactants portionwise to the other with stirring and thereafter heating, if necessary, to bring about the salt formation. The crude reaction products so obtained are adapted to be employed as constituents of fnngicidal and bactericidal compositions without further puriflcation. However, the majority of the salts are crystalline in nature and are readily isolated in substantially clear form by crystallization from benzene, toluene, alcohol, or other suitable organic solvent.

Where it is desired to impregnate solid carriers with the amine salt, the carrier may be introduced into the salt reaction mixture and the phenolate precipitated directly in and On the carrier surfaces. An alternate procedure consists of first wetting a solid finely-divided carrier with one of the toxicants, e. g. the halo-phenol, dissolved in a suitable organic solvent and there kerosene.

after contacting the mixture with a solution of the second reactant, e. g. the amine, to produce EXAMPLE 8--N- [3- (4-CHLOROPHENOXY) -2 -Msrn- YL-PROPYL] CYoLoHExYLAmmn SALT or 2.3.4.6-

TETRACHLOROll-IENOL 11.6 grams (0.05 mole) of 2.3.4.6-tetrachlorophenol and 14.1 grams (0.05 mole) of N-[3-(4- chlorophenoxy)-2-methyl-propyl] cyclohexylamine were mixed together. Heat of reaction was evolved, and the resultant viscous material was warmed on a hot plate to form a free-flowing brown liquid. This product was cooled to obtain a quantitative yield of the N-[3-(4-chlorophenoxy)-2-methyl-propyl] cyclohexylamine salt of 2.3.e.6-tetrachlorophen0l as a resinous solid, soluble in per cent ethyl alcohol, carbon tetrachloride, and hot kerosene, and insoluble in cold At 25 C. this compound was soluble in water to the extent'of only 0.0078 gram per grams oi-solution. The saturated aqueous solution had a pH of 6.53 at 24.6" e.

' benzene.

EXAMPLE 9-'-N.N-DI [2 l CHLOROPHENOXY) Erma] CYCLOHEXYLAMINE Sam on Pan-racmoaornsnor.

40.0 grams (0.1 mole) of NN-di-[2-(4-chlorophenoxy)-ethyll cyclohexylamine dissolved in 25 milliliters of hot benzene was added portion-wise and with stirring to a solution of 26.7 grams (0.1 mole) of pentachlorophenol in 40 milliliters of hot Heat of reaction was evolved and a dark. green color developed in the reaction mixture. Upon stirring and cooling a heavy crop of light green crystals precipitated. These were gram per 100 grams of solution. The saturated aqueous solution had a pH of 6.48 at 345 C.

EXAMPLE BETA (2.4.6 TRICHLOROPHENOXY) BETA-CYCLOHEXYLAMINO-DIETHYL Err-ma SALT or PENTACHLOROPHENOL 26.7 grams (0.1 mole) of pentachlorophenol and 36.7 grams (0.1 mole) of beta-(2.4.6-trichlorophenoxy)-beta-cyclohexylamino-diethyl ether were mixed together with stirring. Heat was evolved from the mixture, and the pentachlorophenol partially dissolved in the amine. 30 milliliters of benzene was added to the mixture, and the latter warmed and stirred to form a dark colored solution. Thus crude product was cooled for hours, filtered, and the residue washed with benzene and air-dried to obtain 33 grams of the beta- (2.4.6-trichlorophenoxy)beta cyclohexylaminodiethyl ether salt of pentachlorophenol as a white crystalline compound melting at 120-l22 C. This salt was soluble in carbon tetrachloride and kerosene and slightly soluble in 95 per cent ethyl alcohol. At 25 C. the compound had a water solubility of 0.0211 gram per 100 grams of solution. The saturated aqueous solution had a pH of 6.62 at 345 C.

EXAMPLE ll-N [2 (2 XENOXY) ETHYL] 2- METHYLCYCLOHEXYLAMINE SALT or 2.4.5-Tiu- CHLOROPHENOL 19.8 grams (0.1 mole) of 2.4.5-trichlorophenol and 30.9 grams (0.1 mole) of N-[2-(2-xenoxy)- ethyl] Z-methylcyclohexylamine were mixed together and warmed to obtain a light yellow liquid reaction product. Upon cooling and standing for 48 hours a quantitative yield of the N-[2-(2- xenoxy)-ethyl] 2-methylcyclohexylamine salt of 2.4.5-trichlorophenol was obtained as a golden yellow viscous syrup soluble in ethyl alcohol, carbon terachloride, and kerosene. In water at 25 C. this compound was soluble to the extent of 0.015 gram per 100 grams of solution. The saturated aqueous solution had a pH of 6.66 at 30.8 C.

In a similarfashion other amines and phenols may be substituted for those shown above to obtain amine salt compounds of which the following are representative:

N- [3- (4-tertiarybutylphenoxy) -2-methyl-propyl] cyclohexylamine salt of 3.5.x-trichloro-2-hyand soluble in carbon tetrachloride, kerosene,

and hot 95 per cent ethyl alcohol. This compound is soluble'in water at 25 C. to the extent of 0.0198 gram per 100 grams of solution. A

saturated aqueous solution at 34.5" C. had a pH Beta-(2-cyclohexylphenoxy) beta cyclohexylamino-diethyl ether salt of 3.5.x-trichloro-2- hydroxy-diiphenyl, a tacky resin-like material soluble in canbon tetrachloride, kerosene, and hot 95 per cent ethyl alcohol. This compound is soluble in water to the extent of 0.0222 gram per 100 grams of solution at 25 C. A saturated aqueous solution at 30.8 C. had a pH of 6.32.

. Beta-phenoxy-beta' cyelohexylamino diethyl ether salt of 2.3.4.6-tetrachlorophenol, a white crystalline compound melting at 102103 C. and soluble in per cent ethyl alcohol, carbon tetrachloride, and hot kerosene. The water solubility of this salt at 25 C. was 0.0118 gram per grams of solution. At this temperature the saturated solution had a pH of 6.83.

Beta- (4 chlorophenoxy) beta cyclohexylamino-diethyl ether salt of 2.3.4.6-tetrachlorophenol, a white crystalline compound melting at 102-106? C. and solublein water at 25 C. to the extent of 0.0058 gram per 100 grams of solution. The saturated aqueous solution had a pH- of 6.38. The compound is soluble in carbon tetrachloride, 95 per cent ethyl alcohol, and hot kerosene.

N- [3 (4 tertiarybutylphenoxy) 2 methylpropyl] cyclohexylamine salt of 2.3.4.6-tetrachlorophenol, a white crystalline compound melting at 137-140 C. and soluble in carbon tetrachloride, kerosene, and 95 ;per cent ethyl alcohol. This salt is soluble in water to the extent of 0.0038 gram per 100 grams of solution at 25 C. At this same temperature the pH of the saturated aqueous solution was 6.34.

N-[2-(4 chlorophenoxy) ethyl] cyclohexylamine salt of 2.3.4.6-tetrachlorophenol, a crystalline compound melting at 104-105 C. and soluble in 95 per cent ethanol, kerosene, carbon tetrachloride, and benzene. The solubility of the salt in water at 25 C. was 0.0091 gram per 100 grams of solution. This saturated solution had a pH of 6.73.

N.N-di- [2- (4-chlorophenoxy) -ethyl] cyclohexylamine salt of 2.3.4.6-tetrachlorophenol, a pale yellow crystalline compound melting at 99-10l C. and soluble in carbon tetrachloride, 95 per cent ethyl alcohol, and hot kerosene. The salt was soluble in water at 25 C. to the extent of 0.0051 gram per 100 grams of solution. The pH of a saturated aqueous solution of the compound at 32 C. was 5.46.

The amine salts of the halophenols described above are relatively non-toxic to humans as compared with many inorganic fungicides containing lead, mercury, cyanide, copper, etc., as at present employed. They are non-explosive and dimcultly flammable. Numerous instances in which they have been contacted with the skin of humans indicate that they are relatively noncorrosive and not inclined to produce dermatitis.

We claim:

l. A fungicidal composition comprising an inert diluent and as an active ingredient a compound of the formula eH1r-NHz-w[(C,.Hz.O) ,..R]

(cyclic) Y o-z wherein R represents an aromatic radical of the benzene series, R is selected from the class consisting of alkyl radicals containing from 1 to 8 carbon atoms, inclusive, phenyl, cyclohexyl, and hydrogen radicals, w is an integer not greater than 2, m is an integer not greater than 4, n is an integer from 2 to 4, inclusive, and Z is a haloaromatic radical of the benzene series having at least one halogen atom directly attached to the oxygenated benzene ring,

2. A fungicidal composition comprising an inert diluent and as an active ingredient a compound of the formula wherein R. represents an aromatic radical of the benzene series, B. is selected from the group consisting of alkyl radicals containing from 1 to 8 carbon atoms, inclusive, phenyl, cyclohexyl, and hydrogen radicals, w is an integer not greater than 2, m is an integer not greater than 4, n is an integer from 2 to 4, inclusive, and z is an integer not greater than 5.

3. A fungicidal composition comprising an inert diluent and as an active ingredient a compound of the formula cm-cm H- i C NH. II I ,H' -R] I wherein It represents an aromatic radical of the benzene series, w is an integer not greater than 2, m is an integer not greater than 4, and a: is an integer not greater than 5.

5. A fungicidal composition comprising an inert diluent and as an active ingredient a compound of the formula Hr-cn, H

01.. wherein w is an integer not greater than 2, m. is an integer not greater than 4, and a: is an integer not greater than .5.

6. A fungicidal composition comprising an inert diluentand as an active ingredient a compound or the formula V GHQ-CH3 H car-Q, 6

wherein R represents an aromatic radicaici the benzene series, w is an integer not greamr than 2-, n is an integer from 2 to 4, inclusive, and a: is an integer not greater than 5.

,7. A fungicidal composition comprising an inert diluent and as an active ingredient a com-'- pound of the formula HrCH: a 0%. c-Nmcme-o-a ennet, r

benzene series. and :c is an integer not greater I than ii.

8. A fungicidal composition comprising an inert diluent and as an active ingredient a com- CHI-C (LG wherein R represents an aromatic radical of the benzene series, and a: is an integer not greater than 5. i

9. A fungicidal composition comprising an inert diluent and as an active ingredient a compound of the formula CHr-C 2 l a l I wherein It represents an aromatic radical of the benze series, w is an integer not greater than 2. and m is an integer not greater than a.

10. A fungicidal composition comprising an inert diluent and as an active ingredient a compound of the formula wherein R represents an aromatic radical of the benzene series, w is an integer not greater than 2, and ,m is an integer not greater than 4.

11. A fungicidal composition comprising an inert diluent and as an active ingredient a compound of the formula cat-cm H C\a c-NHh[-(c,m-o).-a1t

wherein it represents an aromatic radical or the whereinR represents an aromatic radical of the benzene series, to is an integer not greater than 2,

and m is an integer not greater than 4.

12. An amine saltof a halophenol having the formula R C liH\0- 8- nt' 0 min- GPR] in y z wherein R represents an aromatic radical of the benzene series, B. is selected from the class consisting of alkyl radicals containing from i to 8 carbon atoms, inclusive, phenyl, cyclohexyl, and hydrogen radicals, w is an integer not greater than 2, m is an integer not greater than 4, n is an integer from 2 to 4, inclusive, and Z is a haloaromatic radical of the benzene series having at least one halogen atom directly attached to the oxygenated benzene ring.

' GERALD H. COLEMAN.

j GERALD A. GRIESQ. 

